KR102415829B1 - Modified sulfur and method for preparing same - Google Patents

Abstract

The present specification, including sulfur and a modifier, wherein the modifier is an unsaturated fatty acid-based modifier relates to modified sulfur and a method for producing the same.

Description

Modified sulfur and method for preparing same

The present specification relates to an environmentally friendly modified sulfur and a manufacturing method thereof.

Sulfur has a flash point of 207°C and a spontaneous ignition temperature of 245°C. Sulfur has ignitable properties, and sulfur exposed to the surface and in contact with air is easily combusted. It also occurs frequently in the desulfurization process of natural gas.

Sulfur, which is in a stable solid state, has high strength if there is no defect in the sulfur itself, but in the case of solid sulfur formed by cooling and solidifying liquid sulfur, there are generally three types of orthorhombic, monoclinic, and amorphous types mixed. . The solid sulfur solidified in this way changes the mixing ratio of the three types according to the cooling conditions, and the solidified sulfur itself is prone to defects over time and has brittleness that is easy to break. Therefore, pure sulfur has a very limited scope of application.

In particular, it can be applied to various building and civil engineering materials, but there is a limit to the application only with pure sulfur due to the above characteristics. Specifically, in the case of a sulfur material with brittle fracture characteristics, plastic deformation hardly occurs, so all of the force applied to the material is used for destruction as it is, and when a force greater than the yield strength is applied, instantaneous failure occurs. It is an unstable material similar to Portland concrete properties.

In order to improve these shortcomings, various types of sulfur modifiers have been studied. In particular, dicyclopentadiene (DCPD) is known to have an effect such as improving the brittleness of sulfur as well as excellent economic feasibility due to its low price.

However, the reaction of dicyclopentadiene and sulfur is known to be difficult to control because it is difficult to control the polymerization reaction itself, and thus there is a risk of causing an explosive exothermic reaction, and the temperature and viscosity are rapidly increased during the reaction.

In particular, when the reaction is carried out beyond the appropriate polymerization reaction range, a rubber-like phenomenon may occur, which causes damage to the reactor used for the polymerization reaction, which is a dicyclopentadiene-based modifier and sulfur It is known to significantly impair the commercial use of sulfur modifiers prepared from In addition, dicyclopentadiene and sulfur cause supercooling even after the polymerization reaction, making them inefficient in manufacturing and utilization, and dicyclopentadiene and sulfur are environmentally harmful and have a strong foul odor when applied to actual road construction. It was difficult to maintain a constant quality due to the influence of

Korean Patent Publication No. 10-2014-0000160

In order to solve problems such as environmental harmful elements and odors of the existing modified sulfur, the present invention was to develop a modified sulfur that uses an eco-friendly material and has improved high-functionality characteristics.

An exemplary embodiment of the present specification provides a modified sulfur that includes sulfur and a modifier, wherein the modifier is an unsaturated fatty acid-based modifier.

In addition, an exemplary embodiment of the present specification includes a first step of mixing sulfur and an unsaturated fatty acid-based modifier; a second step of putting the mixture into a reactor and melting it by heating it to a temperature of 100°C or higher and 130°C or lower; a third step of raising the temperature of the melt to a temperature of 130 °C or higher and 200 °C or lower; and a fourth step of terminating the reaction when the viscosity of the melt becomes 6,000 cP or more and 25,000 cp or less at 160 °C.

Finally, an exemplary embodiment of the present specification provides a concrete composition comprising the modified sulfur and aggregate.

Reformed sulfur according to an exemplary embodiment of the present specification is environmentally friendly by excluding or minimizing the modifier of petroleum-derived components and replacing the modifier of natural-derived components.

In addition, the modified sulfur according to an exemplary embodiment of the present specification has high functional properties having excellent adhesion, chemical resistance, salt resistance, waterproofness, rust prevention, watertightness, flow resistance, balance resistance, and the like.

1 is a view showing a flow chart for a method for manufacturing reformed sulfur according to an embodiment of the present specification.
2 is a view showing the results of the wheel tracking test of Example 1 and Comparative Examples 1-2 and Comparative Examples 1-3.
3 is a diagram illustrating the measurement of water absorption in Example 4-1 and Comparative Example 4-1.
4 is a diagram comparing the chemical resistance of Examples 5-1 to 5-3 and Comparative Example 5-3.
5 is a diagram illustrating a microstructure photograph (x750) of modified sulfur according to an exemplary embodiment of the present specification.

Best mode for carrying out the invention

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Hereinafter, the present invention will be described in detail.

reformed sulfur

An exemplary embodiment of the present invention provides a modified sulfur comprising sulfur and a modifier, wherein the modifier is an unsaturated fatty acid-based modifier.

In an exemplary embodiment of the present invention, the viscosity of the modified sulfur is 4,000 cP or more and 25,000 cP or less at room temperature. Specifically, in an exemplary embodiment of the present specification, the viscosity of the modified sulfur may be 6,000 cP or more and 10,000 cP or less at room temperature.

In the present specification, the sulfur includes ordinary sulfur, and examples of the sulfur include natural sulfur or sulfur obtained by desulfurization of petroleum or natural gas. As the sulfur of the present invention, sulfur in a solid state may be heated above its melting point to facilitate the reaction, or sulfur discharged in liquid form in related industries such as petrochemicals may be used. In addition, waste sulfur mixed with impurities from the steel mill can be used through simple filtering.

In the present specification, the unsaturated fatty acid-based modifier may refer to a compound including at least one carboxylic acid group and at least one carbon-carbon double bond in the compound.

In one embodiment of the present specification, the unsaturated fatty acid-based modifier may be a material obtained by recycling a fatty acid or unsaturated fatty acid used after using a fatty acid or an unsaturated fatty acid, or may be a material derived from nature. Therefore, as in the exemplary embodiment of the present specification, when the unsaturated fatty acid-based modifier is included, it is more environmentally friendly than when the conventional petroleum product modifier is included.

In one embodiment, the modifier is erucic acid, palmitoleic acid, elaidic acid, myristoleic acid, linoleic acid, arachidone Arachidonic acid, gondoic acid, Oleic acid, Eicosapentaenoic acid, Docosahexaenoic acid DHA, α-Linolenic acid, It is one or more selected from the group consisting of γ-linolenic acid (γ-linolenic acid, GLA) and vegetable oil.

In one embodiment, the vegetable oil, cypress oil, lemon oil, rose oil, lavender oil, sunflower seed oil, corn oil, mustard oil, castor oil, olive oil, cottonseed oil, macadamia (Macadamia integrifolia) oil, It may be selected from the group of oils extracted from natural vegetable oils, such as flaxseed oil, pine oil, hippophae rhamnoides oil, lunaria biennis oil, and canola oil.

In an exemplary embodiment of the present specification, the content of the modifier is 10 parts by weight or more and 450 parts by weight or less based on 100 parts by weight of the sulfur. Specifically, the content of the modifier may be 30 parts by weight or more and 300 parts by weight or less, based on 100 parts by weight of sulfur. When the content of the modifier is less than 10 parts by weight based on 100 parts by weight of the sulfur, it is difficult to maintain a liquid state after synthesis, the functionality of the modified sulfur cannot be expected, and the brittleness of the sulfur remains, so there is a difficult problem in use. In addition, when the content of the modifier exceeds 450 parts by weight based on 100 parts by weight of the sulfur, there is no brittleness of sulfur, but the functionality such as waterproofing, rust prevention, adhesion and chemical resistance of the modified sulfur may be significantly reduced.

In another exemplary embodiment, the modified sulfur has spinnability. In the present invention, spinnability can be expressed as stringiness, thread pullability, etc., and whether or not it has spinnability is an experiment in which a glass stick is put into a mixture or reactant in a solution state in the manufacturing process of modified sulfur and then removed The case where a part of the mixture or reactant in a solution state is connected to a glass rod and pulled out like a long thread (1 cm or more) is observed to be defined as that the mixture or reactant has spinnability can

In one embodiment, the modified sulfur includes a network structure or a honeycomb structure. The modified sulfur according to an exemplary embodiment of the present specification may include an unsaturated fatty acid-based modifier, so that double bonds in the unsaturated fatty acid-based modifier may be cross-linked in a honeycomb structure or a network structure through a polymerization reaction. In this case, it is possible to improve the functionality of the modified sulfur, such as adhesion, chemical resistance, flame resistance, rust prevention, watertightness, flow resistance, high strength.

5 is a diagram illustrating a microstructure photograph (x750) of modified sulfur according to an exemplary embodiment of the present specification. 5, it can be confirmed that the modified sulfur according to an exemplary embodiment of the present specification includes a microstructure, and specifically, it can be confirmed that the modified sulfur according to an exemplary embodiment of the present specification includes a fibrous tissue.

In another embodiment, the modified sulfur is amphiphilic. Modified sulfur according to an exemplary embodiment of the present specification may provide amphiphilic modified sulfur by including an unsaturated fatty acid-based modifier.

Waterproofing is required to prevent rusting and corrosion of metal surfaces and to prevent leaks, cracks, and durability of structures such as buildings. Existing waterproofing and rust-preventing materials have difficulties in the repeated coating film formation process, workability, and environmental hazards.

The solid modified sulfur with rubberized high viscosity has excellent chemical resistance and adhesion enough to be used as a substitute for Epoxy Fiber-reinforced Plastic (FRP). In order to be used for construction and repair and reinforcement of structures, a separate device such as a heating spray is required for high-temperature pretreatment for melting of reformed sulfur.

The modified sulfur according to an exemplary embodiment of the present specification may be an amphiphilic modified sulfur having hydrophilic and hydrophobic properties. The modified sulfur can be used for road pavement and repair reinforcement and polymer concrete compositions without preheating and heating processes by mixing only the modified sulfur and aggregate in a liquid phase at room temperature due to hydrophobic properties. In addition, due to the hydrophilic property, water and aggregate, the modified sulfur binder and hydraulic materials are added and mixed at room temperature, for example, a small amount of a water reducing agent, an antifoaming agent, and a mold release agent. .

In one embodiment of the present specification, the modified sulfur may be in a liquid phase. In this case, miscibility and dispersibility with the material is excellent, a separate heating process is not required when mixing with the hydraulic material, and excellent reforming effect can be obtained even with a small amount. However, if necessary, the modified sulfur may be subjected to various modifications, and may be applied in various forms, for example, solid, pellet, powder, and the like.

In another exemplary embodiment, the modified sulfur further includes an additional second modifier different from the unsaturated fatty acid-based modifier.

In one embodiment, the second modifier may be one or two or more selected from the group consisting of a saturated fatty acid-based modifier, an unsaturated fatty acid-based modifier, an alcohol-based modifier, an ester-based modifier, and a dicyclopentadiene-based modifier. have.

The second modifier may be optionally added depending on the use when synthesizing the modified sulfur.

In the exemplary embodiment of the present specification, the saturated fatty acid-based modifier includes, but is not limited to, stearic acid, palmitic acid, and the like.

In an exemplary embodiment of the present specification, the unsaturated fatty acid-based modifier includes oleic acid, but is not limited thereto.

In one embodiment, the alcohol modifier, glycerol (glycerol), etc., but is not limited thereto.

In the present specification, the ester-based modifier includes, but is not limited to, wax ester, dihydrocholesteryl oleate, and the like.

In the present specification, the dicyclopentadiene-based modifier refers to a dicyclopentadiene-based modifier containing a cyclopentadiene oligomer. Dicyclopentadiene (DCPD, dicyclopentadiene) is a dimer of cyclopentadiene (CPD), which can be generated during the thermal decomposition of naphtha, and is applicable to commercially available products containing dicyclopentadiene. can

Specifically, the dicyclopentadiene-based modifier includes: 1) dicyclopentadiene (DCPD); 2) at least one selected from the group consisting of cyclopentadiene (CPD), DCPD derivatives and CPD derivatives (methyl cyclopentadiene (MCP), methyl dicyclo pentadiene (MDCP)) and a mixture of dicyclopentadiene; 3) At least one selected from the group consisting of olefin compounds such as dipentene, vinyl toluene, styrene monomer, and dicyclo pentene, and a mixture of 1) or 2) above can

In an exemplary embodiment of the present specification, the content of the second modifier may be 0.01 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of sulfur. The content range of the second modifier may be specifically adjusted according to characteristics such as adhesion, hydrophobicity, waterproofness, and rust prevention according to the use of the modified sulfur.

Specifically, when the dicyclopentadiene-based modifier is used as the second modifier, the content of the dicyclopentadiene-based modifier is 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of sulfur. In addition, when using a saturated fatty acid-based modifier, an unsaturated fatty acid-based modifier, an alcohol-based modifier or an ester-based modifier as the second modifier, the content of the second modifier is 10 parts by weight or more, 300 parts by weight based on 100 parts by weight of sulfur. is below.

When the second modifier is a dicyclopentadiene modifier, when the content of the dicyclopentadiene modifier is less than 0.01 parts by weight based on 100 parts by weight of sulfur, it is difficult to provide the desired functionality of the modified sulfur, and When the content of the clopentadiene-based modifier exceeds 5 parts by weight based on 100 parts by weight of sulfur, the desired functionality of the modified sulfur may be provided, but it is difficult to apply to the field due to environmental risks and unpleasant odors. More specifically, when the second modifier is dicyclopentadiene (DCPD), based on 100 parts by weight of sulfur, when the DCPD exceeds 100 parts by weight, the synthesis is caused by an explosion of DCPD during the synthesis reaction of the modified sulfur. It is not easy, and it may have a viscosity of 10,000 cP or more, which is the viscosity after synthesis, but it is difficult to use if heat is not applied in the form of a solid after cooling, and it is almost impossible to apply in the field due to a strong foul odor.

In one embodiment of the present specification, the modified sulfur may further include one or two or more selected from the group consisting of an initiator, a surfactant, a coupling agent, a catalyst, an additive, a crosslinking agent, and a dispersing agent.

Specifically, the initiator, surfactant, coupling agent, catalyst, additive, crosslinking agent, and dispersing agent are generally applicable as long as they do not interfere with the polymerization reaction of the modified sulfur of the present invention, and any material classified by the above name can be applied, and special not limited to The initiator, surfactant, coupling agent, catalyst, additive, crosslinking agent and dispersing agent may improve the dispersibility of the modified sulfur or form a hydrophilic or hydrophobic reactive group of the modified sulfur, and modified sulfur produced by polymerization reaction It may play a role in inhibiting or promoting crosslinks within.

In one embodiment of the present specification, the initiator may be one or two or more selected from the group consisting of sulfur, modified sulfur, asphalt, sulfide, polysulfide, and hydrocarbon compound. The initiator may be added simultaneously with the modifier or separately during the reaction. When the initiator is sulfur, it can be applied as an initiator by adding it while the reaction is in progress.

As the initiator, the sulfur may be elemental sulfur, crystalline sulfur, amorphous sulfur, colloidal sulfur, and mixtures thereof. In addition, the sulfur may be any one selected from the group consisting of α-sulfur (orthorhombic sulfur), β-sulfur (monoclinic sulfur), γ-sulfur, and combinations thereof. The asphalt refers to straight asphalt or modified asphalt, and the sulfides are compounds containing sulfur, and may include, but are not limited to, carbon disulfide. The polysulfide (polysulfide) may include, but is not limited to, a polysulfide-modified epoxy resin. The hydrocarbon compound refers to a compound composed of carbon and hydrogen, and includes straight-chain, branched-chain, cyclic, and aromatic hydrocarbon compounds. The initiator may be a pre-polymerized modified sulfur, and is not limited to a modified sulfur prepared by a specific manufacturing method.

In an exemplary embodiment of the present specification, the initiator is trans Cinnamaldehyde, Benzyl Acetate, Diethylaniline, Nitroethane, Formaldehyde Hydrate. , benzyl acetate (Benzyl Acetate), dodecyl benzene sulfonic acid (Dodecyl benzene sulfonic acid), cetyltrimethylammonium bromide (CTMAB), methylmorpholine (Methylmorpholine) and morpholine (Morpholine), the group consisting of dimethylaniline (Dimethylaniline) It may be one or two or more selected from.

The initiator may be used alone, or a mixture of two or more different initiators may be used, and an initiator not exemplified above may be used together with the initiator.

The initiator may serve to promote or control a polymerization reaction between the unsaturated fatty acid-based modifier and the sulfur.

In the exemplary embodiment of the present specification, the content of the initiator may be 0.01 parts by weight or more and 2 parts by weight or less per 100 parts by weight of sulfur.

In an exemplary embodiment of the present specification, the initiator may control the characteristics of the modified sulfur produced by changing the specific type, addition amount, input timing, reaction conditions, etc. of the applied initiator.

In the present specification, the surfactant may be one or more selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

The anionic surfactant includes sulfate-based anionic surfactants, sulfonate-based anionic surfactants, and other anionic surfactants. The sulfate-based anionic surfactants include alkyl sulfate, alkylester-sulfate, alkyl ether sulfate, and alkyl-ethoxy-ethersulfate. ); sulfated alkanolamide; glyceride sulfate and the like may be included, but the present invention is not limited thereto. The sulfonate-based anionic surfactant includes dodecyl benzene sulfonate including ABS (alkyl benene sulfonate) and LAS (linear alkyl benzene sulfonate); hydrotropes, short tail alkyl-benzene sulfonate; alpha-olefin sulfonates; lignosulfonate; A sulfo-carboxylic compound including sodium lauryl sulfoacetate may be included, but the present invention is not limited thereto. The other anionic surfactants include organo phosphored surfactants; It may include, but is not limited to, an alkyl amino acid including lauryl sarcosinate, sarcosine, and the like.

The cationic surfactant includes a linear alkyl-amine containing a fatty amine, a linear alkyl-ammonium containing a quaternary alkyl ammonium, and a thiol Diamine (linear diamine), n-dodecyl pyridinium chloride (n-dodecyl pyridinium chloride), imidazole (imidazole), morpholine compound (morpholine compound) and the like may be included, but is not limited thereto.

Examples of the nonionic surfactant include ethoxylated alcohol, alkylphenol, fatty acid ester, and nitrogen-based nonionic surfactant. Examples of the ethoxylated alcohol and alkyl phenol type nonionic surfactant include ethoxylated linear alcohol, ethoxylated alkyl phenol, and ethoxylated alkyl phenol. It may include, but is not limited to, ethoxylated thiol, nonylphenol, octylphenol, and the like. The fatty acid ester-based nonionic surfactant may include polyethoxy ester, glycerol ester, hexitol, cyclic anhydrohexitol ester, and the like, It does not limit this. The nitrogen-based nonionic surfactant includes ethoxylated amine, imidazole, cyclic alkyl-diamine, ethoxylated alkyl-amide, tertiary. It may include, but is not limited to, amine oxide (tertiary amine oxide).

The amphoteric surfactant may include amino propionic acid, imino propionic acid, quaternized compound, and the like, and examples of the quaternized compound include sulfobetaine. surfactants, and the like, but are not limited thereto.

In the present specification, when the surfactant is selected and applied according to the use of the modified sulfur, specific functionality required according to the use in the preparation of the modified sulfur may be improved.

In the present specification, the coupling agent may be one or more selected from the group consisting of a silane-based coupling agent, a titanate-based coupling agent, and a chromium-based coupling agent, and a surfactant used in the art may be used.

The silane-based coupling agent includes a sulfide-based silane compound, a mercapto-based silane compound, a vinyl-based silane compound, an amino-based silane compound, a glycidoxy-based silane compound, a nitro-based silane compound, a chloro-based silane compound, a methacryl-based silane compound, and these compounds. Any one selected from the group consisting of a combination of may be applied, but is not limited thereto.

The titanate-based coupling agent is isoprosyltriisostearoyltitanate, isopropyl tridodecylbenzenesulfonyltitanate, isopropyltri(dioctylpyrophosphate)titanate, tetraisopropyldi(drideensylphos) Any one selected from the group consisting of phite) titanate, tetraisopropyl di(dioctylphosphite) titanate, tetraoctyloxytitanium (ditridensylphosphite), and combinations thereof may be applied, but is not limited thereto.

When the coupling agent is applied in the present specification, it is possible to improve the interfacial adhesion of the modified sulfur, and when mixed with a different material, the adhesion to the dissimilar material may be improved, and it may be advantageous for forming a composite material.

In the present specification, the additive may be an inorganic or resin additive, and specifically, silica sand, diatomaceous earth, wollastonite, clay, chopped glass fiber, dye, pigment, aluminum sulfate, water glass, Ca(OH) ) ₂ , zinc oxide, naphthalene, Mg(OH) ₂ , CaCl ₂ , Al(OH) ₃ , borax, CaSO _4.2H2O , Fe ₂ O ₃ , zeolite, carbon black, talc, carbon fiber, clay, whisker ), Na ₂ SO ₃ , MgSO _4.7H2O , fly ash, acrylic emulsion, epoxy, latex, carbon fiber or sheet, steel fiber, liquid mineral, titanium dioxide, fibrous filler, fibrous particles, flaky particles and It may be one or two or more types selected from the group consisting of a combination of shredded recycling wastes.

In an exemplary embodiment of the present specification, the additive may be 0.1 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the sulfur.

As the crosslinking agent, a sulfur-based crosslinking agent, an organic peroxide, a resin crosslinking agent, and a metal oxide such as magnesium oxide may be used. The sulfur-based crosslinking agent includes an inorganic crosslinking agent such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), and colloidal sulfur, and tetramethylthiuram disulfide (TMTD), tetraethylthiuram An organic crosslinking agent such as disulfide (tetraethyltriuram disulfide, TETD) or dithiodimorpholine may be used, but is not limited thereto. As the sulfur crosslinking agent, elemental sulfur or a vulcanizing agent for generating sulfur, for example, amine disulfide, polymeric sulfur, etc. may be used, but is not limited thereto. The organic peroxide is benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di ( t-Butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3- Bis(t-butylperoxypropyl)benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1-dibutylperoxy-3 Any one selected from the group consisting of ,3,5-trimethylsiloxane, n-butyl-4,4-di-t-butylperoxyvalerate, and combinations thereof may be used, but is not limited thereto.

The dispersant may be used to improve miscibility when mixing the modified sulfur and the surfactant, the modified sulfur and the coupling agent, or the modified sulfur and the reinforcing material. The dispersant can be applied as long as it can improve the degree of dispersion when mixing the modified sulfur with a surfactant, a coupling agent, a reinforcing material, etc. It can act as a dispersant to the extent that it serves to improve the

As the dispersant, any one polymer dispersant selected from the group consisting of polyvinylpyrrolidone, polyethyleneimine, polyacrylic acid, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyethylene oxide, starch, gelatin, and combinations thereof Applicable, but not limited thereto.

One or two or more selected from the group consisting of the initiator, surfactant, coupling agent, catalyst, additive, crosslinking agent, and dispersing agent may be mixed with the modified sulfur in a solvent.

As the solvent, a conventional solvent may be applied as long as it helps to mix the modified sulfur with the initiator, surfactant, coupling agent, catalyst, additive, crosslinking agent and/or dispersant and does not interfere with the polymerization reaction of the modified sulfur. It does not limit this.

The solvent is water, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an ether solvent, an alcohol solvent, a polyol solvent, an amide solvent, an acetate solvent, a non-aqueous inorganic solvent, an amine solvent, an ester solvent, a ketone solvent. It may be one or two or more selected from the group consisting of a solvent and a sulfone-based solvent.

Examples of the aliphatic or aromatic hydrocarbon-based solvent include toluene, xylene, aromasol, chlorobenzene, hexane, heptane, octane, dodecane, cyclohexane, decane, tetradecane, and hexadecane. It may be any one selected from the group consisting of decane, octadecane, octadecene, nitrobenzene, o-nitrotoluene, anisole, mesitylene, and combinations thereof, but is not limited thereto.

Examples of the ether-based solvent include diethyl ether, dipropyl ether, dibutyl ether, dioxane, tetrahydrofuran, diisobutyl ether, isopropyl ether, octyl ether, tri( Ethylene glycol) may be any one selected from the group consisting of dimethyl ether and combinations thereof, but is not limited thereto.

Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, hexanol, isopropyl alcohol, ethoxyethanol, ethyl lactate, octanol isopropyl alcohol, Ethylene glycol monomethyl ether, benzyl alcohol, 4-hydroxy-3-methoxy benzaldehyde, isodeconol, butylcarbitol, terpineol, alpha terpineol, beta-terpineol, cineol and It may be any one selected from the group consisting of combinations thereof, but is not limited thereto.

Examples of the polyol solvent include glycerol, glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexylene glycol, 1,2-pentadiol, 1,2-hexadiol , glycerin, polyethylene glycol, polypropylene glycol, ethylene glycol monomethyl ether (methyl cellusolve), ethylene glycol monoethyl ether (ethyl cellusolve), ethylene glycol monobutyl ether (butyl cellusolve), diethylene glycol monoethyl ether, It may be any one selected from the group consisting of diethylene glycol monobutyl ether and combinations thereof, but is not limited thereto. [0128] The amide-based solvent may be any one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone, N,N-dimethyl acetamide, and combinations thereof, It does not limit this.

Examples of the amine solvent include primary amines such as propylamine, n-butylamine, hexylamine, and octylamine, secondary amines such as diisopropylamine and di(n-butyl)amine, trioctylamine, and tri-n - Any one selected from the group consisting of tertiary amines such as butylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, trioctylamine, etc., cyclic amine, aromatic amine, and combinations thereof can, but is not limited thereto.

Examples of the ester solvent include PEGMEA, ethyl acetate, n-butyl acetate, γ-butyrolactone, 2,2,4-trimethylpentanediol-1,3-monoisobutyrate, butyl carbitol acetate, butyl oxalate, di It may be any one selected from the group consisting of butyl phthalate, dibutyl benzoate, butyl cellosolve acetate, ethylene glycol diacetate, ethylene glycol diacetate, and combinations thereof, but is not limited thereto.

The ketone-based solvent is from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone, and combinations thereof. It may be any one selected, but is not limited thereto.

The amide solvent may be any one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone, N,N-dimethyl acetamide, and combinations thereof, but is not limited thereto. does not

The sulfone-based solvent may be any one selected from the group consisting of diethylsulfone, tetramethylene sulfone, and combinations thereof, but is not limited thereto.

As the acetate-based solvent, any one acetate-based solvent selected from ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, and combinations thereof may be used.

Carbon disulfide, liquid ammonia, etc. may be used as the non-aqueous inorganic solvent, but is not limited thereto.

In one embodiment of the present specification, the modifier is a binder prepared by melt polymerization with sulfur and a modifier of an eco-friendly material, and is generally in a liquid or gel state at room temperature, and by maximizing polymerization according to the use in the melt polymerization reaction When the modifier in the obtained solid state (powder, pellet) is used as a material for a waterproofing agent and rust preventive agent, the diluent to be mixed is ethanol, methanol, MEK, toluene, m-xylene , p-xylene (P-xylene), etc. may be one comprising any one selected from the group. The use may mean applying by increasing properties such as hydrophobicity, waterproofness, rust prevention, chemical resistance, adhesiveness, and high strength as needed.

Process for the production of reformed sulfur

The present specification also includes a first step of mixing sulfur and an unsaturated fatty acid-based modifier; a second step of putting the mixture into a reactor and melting it by heating it to a temperature of 100°C or higher and 130°C or lower; a third step of raising the temperature of the melt to a temperature of 130 °C or higher and 200 °C or lower; and a fourth step of terminating the reaction when the viscosity of the melt becomes 6,000 cP or more and 25,000 cp or less at 160 °C.

In one embodiment of the present specification, the modified sulfur produced by the manufacturing method may be equally applied as long as it does not contradict the matters mentioned in the above-described modified sulfur.

In an exemplary embodiment of the present specification, the first step of mixing the sulfur and the unsaturated fatty acid-based modifier includes 10 parts by weight or more of the unsaturated fatty acid-based modifier, based on 100 parts by weight of the sulfur, and 450 parts by weight or less. Mix.

In addition, in one embodiment, in the first step, the second modifier may be further included in the above-described content range.

In another exemplary embodiment, one or two or more selected from the group consisting of the initiator, surfactant, coupling agent, catalyst, additive, crosslinking agent and dispersing agent may be further included in the above-described content range.

In one embodiment, the first step may be carried out at a temperature of room temperature (Room Temperature; about 15 ℃ to 25 ℃) or higher.

In an exemplary embodiment of the present specification, the viscosity before heating of the mixture of sulfur and the unsaturated fatty acid-based modifier prepared in the first step is 0 cP at room temperature.

In an exemplary embodiment of the present specification, the second step may be melted by heating to a temperature of 100 ℃ or more, 130 ℃ or less. Specifically, the second step may be melted by heating to an internal temperature of about 120° C., and a polymerization reaction is started.

Specifically, in the second step, the mixture is put into a polymerization reactor, the temperature is set to about 120° C. with a temperature control device of the polymerization reactor, the mixture is administered to the polymerization reactor, and melt polymerization can be started. . In addition, at a temperature of about 120 ℃ of the polymerization reactor, the blades of the reactor are stopped until the sulfur and other mixed materials are sufficiently liquid, and when the mixture is converted to liquid, the blades are rotated to proceed with melt polymerization.

In an exemplary embodiment of the present specification, after the mixture of the second step becomes a liquid phase, a third step of raising the temperature of the liquid mixture may be performed.

In an exemplary embodiment of the present specification, the third step of raising the temperature of the melt may be performed by continuously heating the melt to a temperature of 130 ℃ or more and 200 ℃ or less. Specifically, the third step of raising the temperature of the melt may be performed by continuously heating the melt to a temperature of 130 °C or higher and 180 °C or lower. More specifically, in the third step, when the melt in the second step is converted to a liquid state, the temperature may be raised by setting the temperature device of the polymerization reactor to about 135°C.

In one exemplary embodiment, in the third step of raising the temperature of the melt, the temperature is raised so that the temperature difference between the external temperature of the reactor and the melt is 20° C. or less. Specifically, the temperature of the polymerization reactor may be gradually increased by 2°C to 3°C to about 135°C while the temperature inside the reactor and the outside temperature have little deviation (about 5°C or less). When the temperature increase rate is rapidly increased, the internal temperature of the reactor is rapidly increased due to the exothermic reaction of sulfur and the modifier, making temperature control difficult and carbonization may occur.

In an exemplary embodiment of the present specification, when the temperature of the melt is 160° C. or higher, the fourth step of terminating the reaction may be performed according to the use by measuring the state and viscosity of the melt three or more times per hour. Specifically, when the reaction is terminated at a viscosity of 6,000 cP or more and 15,000 cP or less at 160 °C, the prepared modified sulfur may be for room temperature asphalt and modified sulfur polymer concrete, and the viscosity at 160 °C is 6,000 cP or more, 25,000 cP When the reaction is terminated below, the prepared modified sulfur may be used for a waterproof paint or a rust-preventive paint.

In an exemplary embodiment of the present specification, the viscosity of the melt is 4,000 cP or more and 25,000 cP or less at 135°C.

When the reaction time of the third step is adjusted to be long, it is possible to provide modified sulfur having high viscosity properties that are rubberized. In this case, the modified sulfur can also be used for waterproofing and rust prevention by using a diluent. In addition, when high-viscosity modified sulfur is produced in a solid or powder form, it can be added during the manufacture of roads and concrete structures to provide properties such as waterproofing, rust prevention, high adhesion, and chemical resistance, and using the high-viscosity properties Therefore, it can be applied to a variety of products such as quick fix repair agent, quick fix water repellent agent, waterproof sheet, antibacterial silicone, paint, waterproof and tile adhesive.

In an exemplary embodiment of the present specification, a fourth step of terminating the reaction may be performed when the viscosity of the melt heated in the third step becomes 6,000 cP or more and 25,000 cp or less at 160 °C. That is, in an exemplary embodiment of the present invention, the point at which the viscosity of the melt heated in the third step becomes 6,000 cP or more and 25,000 cp or less at 160° C. may be referred to as the reaction termination time.

In an exemplary embodiment of the present specification, when the reaction is terminated at a time when the viscosity of the melt becomes 6,000 cP or more and 25,000 cp or less at 160 ° C., the modified sulfur has radioactivity, or contains a network structure or a honeycomb structure. can

Specifically, the end of the reaction is the point at which a fibrous or plate-shaped microstructure is observed due to the elevated high adhesiveness of the melt (when a small rod is immersed in a sample, it does not break like a thread (3 cm or more). This can be explained by the phenomenon of stretching into several strands (more than 1cm) as thin as a thread when the finger is put on the disposable silicone glove fingers.

In addition, the reaction termination time may be between the time point at which the reaction is radioactive and the point at which the rubberization of the stage before carbonization proceeds, and the modified sulfur includes a microstructure shape of fibrous, honeycomb structure, and network structure, or radioactive properties. may be having

In the exemplary embodiment of the present specification, when the reaction is terminated in the fourth step of terminating the reaction when the viscosity of the melt becomes 6,000 cP or more and 25,000 cp or less at 160 ° C., the reaction temperature inside the reactor is about 160 ° C. to about 200 °C.

In the fourth step where the reaction is completed, the viscosity of the reactant may be 5,000 cp to 2,000,000 cp at about 160 °C to about 200 °C.

In an exemplary embodiment of the present specification, the method further includes the step of aging after the third step and before the fourth step, wherein the aging step is performed at a temperature of 40° C. or higher for the melt. When the aging step is further included, the reaction termination time of the heated melt of the third step may be adjusted just before it has radioactivity, and the viscosity of the modified sulfur may be adjusted according to the intended use.

Specifically, the aging may be performed at a temperature of 40 °C or higher and 120 °C or lower. More specifically, the aging may start at a temperature of about 40 °C and be performed at an aging temperature of about 120 °C or less. In the aging step, the viscosity may be adjusted according to the use of the modified sulfur.

In the exemplary embodiment of the present specification, the manufacturing method of the modified sulfur, that is, the first to fourth steps, may be about 6 hours to about 18 hours, but may vary depending on the amount of the mixture and the structure or material of the polymerization reactor. can

In the method for producing the modified sulfur, the mixture of sulfur and the modifier undergoes a second polymerization starting step, and a polymerization reaction is gradually made, and in the third step, the melt is yellow, light brown, dark brown, opaque You can go through the process of changing in the order of one black. An initiator may be added between the time the color of the mixture changes, or another initiator may be added just before the reaction is terminated.

In an exemplary embodiment of the present specification, by adjusting the mixture added in the first step, the temperature and time of the polymerization reaction, and the reaction termination time according to the use of the modified sulfur, the shape and/or viscosity of the radioactivity can be adjusted according to the use. have.

In addition, in the exemplary embodiment of the present specification, the characteristics of the modified sulfur may be adjusted by adjusting the input timing, type, and amount of the initiator according to the use of the modified sulfur.

concrete composition

The present specification also includes a concrete composition comprising the aggregate and modified sulfur.

In one embodiment of the present specification, the modified sulfur contained in the concrete composition may be equally applied as long as it does not contradict the matters mentioned in the above-described modified sulfur.

Concrete composition according to an exemplary embodiment of the present specification, by including the modified sulfur, the fluidity is improved, it is easy to mix with the aggregate within a short time. In addition, since the modified sulfur includes a honeycomb structure or a network structure, adhesion, waterproofness, elasticity and/or strength may be improved. In addition, modified sulfur according to an exemplary embodiment of the present specification overcomes the brittleness of sulfur, odor is removed, and is environmentally friendly.

In the present specification, the aggregate may be any one selected from the group consisting of recycled industrial waste, river sand, crushed stone, coal ash, sea sand, silica sand, gravel, silica, quartz powder, lightweight aggregate, clay mineral, glass powder, and combinations thereof. have.

The recycling industrial waste is, for example, a waste stone powder sludge obtained by precipitating stone powder generated when crushing aggregates with a sodium acrylate copolymer polymer coagulant, and is treated as waste and has difficulty in landfilling. Meaning, if it is industrial waste that can be used as the aggregate, it can be applied as the recycled industrial waste, and is not limited to waste stone powder sludge.

It may be applied as a mortar in the case of applying fine aggregate having a particle diameter of 1 to 10 mm as the aggregate, and may be applied to concrete when the fine aggregate and coarse aggregate having a particle diameter of 10 to 18 mm are applied together as the aggregate.

In an exemplary embodiment of the present specification, based on 100 parts by weight of the concrete composition, the content of the modified sulfur may be 1 part by weight or more and 80 parts by weight or less, and the content of the aggregate may be 70 parts by weight or more and 95 parts by weight or less. .

In one embodiment of the present specification, the concrete composition may be a polymer concrete composition, that is, a resin concrete composition.

In an exemplary embodiment of the present specification, the concrete composition may be used alone or in mixture in the field of latex-modified concrete (LMC) or ultra rapid harding cement.

In one embodiment of the present specification, the concrete composition may be a hydraulic polymer concrete composition.

The hydraulic polymer concrete composition according to an exemplary embodiment of the present specification has a hydrophilic property that can be dissolved in water at room temperature. Therefore, the concrete composition can be dissolved in water and used by melting and mixing a water reducing agent, a mold releasing agent, an antifoaming agent, and other modifiers. can

In one embodiment of the present specification, the concrete composition may further include a binder. The binder, for example, latex, lacquer, epoxy (Epoxy), a resin such as MMA (Methyl Methacrylate) may also be used as the binder.

Since the concrete composition according to an exemplary embodiment of the present specification is thermoplastic like conventional asphalt, it can be uniformly mixed through the process of melt mixing.

In one embodiment of the present specification, the concrete composition may further include a filler.

In one exemplary embodiment of the present specification, the content of the filler may be 1 part by weight or more and 60 parts by weight or less, based on 100 parts by weight of the concrete composition.

In the present specification, the filler may be one or more selected from the group consisting of stone powder, portland cement, slaked lime, fly ash, recovered dust, steelmaking dust, reinforcing material, and crushed waste aggregate and powder.

The meaning of waste aggregate and waste powder of the crushed waste resources may mean waste asphalt, waste concrete, waste tires, steelmaking slug, waste plastic, waste glass, waste sand sludge, waste stone powder, waste glass powder, and the like.

In one embodiment of the present specification, the concrete composition may further include a curing agent.

In one embodiment of the present specification, the curing agent may be one type or a mixture of two or more types of generally used curing agents, for example, MgO, cement, etc., but is not limited thereto. In addition, depending on the use, light (Light MgO) and small (Heavy MgO) may be used. Furthermore, by adjusting the amount of the curing agent, it is possible to control the increase or decrease of curing time and strength.

In addition, the present specification may provide a composition comprising the modified sulfur and the curing agent, and the composition including the modified sulfur and the curing agent may be used as a quick-setting repair agent, a quick-setting adhesive, waterproofing, rust prevention, and the like.

In the exemplary embodiment of the present specification, when the curing agent is cement, the content of the curing agent is 10 parts by weight or more and 70 parts by weight or less, based on 100 parts by weight of aggregate.

In the exemplary embodiment of the present specification, when the curing agent is MgO, the amount of the curing agent is 1 part by weight or more and 40 parts by weight or less based on 100 weight of the aggregate.

When the curing agent is cement, the cement can be used for road paving in the field using a ribbon mixer or general ready-mixed concrete at room temperature without adding water. Specifically, the modified sulfur according to an exemplary embodiment of the present specification includes a honeycomb structure and a mesh structure, and thus may contain moisture by itself using a thixotropic phenomenon. Therefore, when using the modified sulfur according to an exemplary embodiment of the present specification containing moisture, it can be poured on the road by a general concrete construction method without a separate water supply, and the curing time of the modified sulfur polymer concrete can be reduced by adjusting the curing agent. It can be adjusted by shortening (1 day to 7 days).

The concrete composition according to an exemplary embodiment of the present specification may be applied to various civil works, building materials, road pavement, repair reinforcement, and emergency repair.

In an exemplary embodiment of the present specification, the room temperature road paving method using the concrete composition (asphalt, asphalt concrete) excludes heating asphalt and heating method road pavement construction, and environmentally friendly mixer ( The road pavement construction using only a mixer) and rollers can be applied, and the concrete composition containing modified sulfur has high adhesiveness, so it is not necessary to apply an initial oil film in the asphalt pavement construction, so the work of prime coating (tack coating) This can be omitted.

In an exemplary embodiment of the present specification, the method of instantaneous construction of the concrete composition at room temperature in the field improves strong adhesion, chemical resistance, waterproofness, rust resistance, high elasticity, strong abrasion resistance, etc. by supplementing the disadvantages of existing asphalt or concrete. As the characteristics of anti-strength asphalt, it is environmentally friendly, low cost, high quality, and shortens the construction period to obtain eco-friendly and economic effects.

In addition, the use of the reformed sulfur for the recycling of industrial and domestic wastes in landfills or incinerators, development of road pavement materials and materials for repair and reinforcement, and production of various modified sulfur polymer concrete structures for waste reprocessing, air pollution and reduction of landfill sites There are great economic advantages, such as fast construction and low cost.

Concrete composition containing liquid modified sulfur according to an exemplary embodiment of the present specification is a ready-mixed concrete mixer without heating equipment by mixing the modified sulfur binder in the field by constructing modified sulfur polymer concrete (semi-strength asphalt) at room temperature by replacing the existing heated asphalt. Simple road construction, repair and reinforcement work can be done only with rollers and rollers.

In addition, the concrete composition according to an exemplary embodiment of the present specification has excellent durability because it has little deformation even in hot climates, and can be constructed without water supply, so it is possible to construct roads in desert areas, mountainous areas, Africa, Middle East Asia, Southeast Asia, etc. It may also be suitable for packaging.

In addition, the existing asphalt construction is difficult to construct in cold winter due to the change in physical properties depending on the difference in external temperature, but the modified sulfur according to an exemplary embodiment of the present specification uses strong characteristics against heat generation and low-temperature cracking, which are sulfur characteristics. Road construction and repair and reinforcement work may be possible even in the weather (before or after minus 5 degrees Celsius).

In particular, for the use of island areas, road construction can be done only with general aggregate and the reformed sulfur, so it is optimal for island areas such as the Philippines, Indonesia, Cuba, and Caribbean coastal areas with many islands and does not require an asphalt batch plant. In addition, recycling of industrial and household wastes in the island area has great help and economic benefits in terms of waste reprocessing and the environment.

Furthermore, if the construction using heat is used in tunnel construction, there are economic benefits such as a small drop-off rate (rebound rate) due to strong adhesion and waterproof properties and shortening of the construction period by omitting the tarpaulin work.

The modified sulfur properties according to an exemplary embodiment of the present specification, which continue to harden even in water, have an excellent effect on sinkhole repair work, and during construction, emergency repairs and emergency roads can be opened easily and open in a short time by adjusting hardening during construction. There is also a range of economic effects.

Due to its strong salt-resistance characteristics, it is possible to use sand or aggregates containing salt (including marine debris), and due to the characteristics of strong adhesion and high strength, it is possible to construct temporary roads with only ordinary soil or sand for temporary pavement.

When using the modified sulfur according to an exemplary embodiment of the present specification, it can be applied to emergency road repair by adjusting the curing time, and when repairing and reinforcing old asphalt roads, use an existing scarifier and remove only the upper layer (5 cm), The removed waste asphalt concrete or waste aggregate is crushed on site (13mm aggregate level), mixed with this reformed sulfur at room temperature, and poured into the upper part of the road to a thickness of 5cm and can be recycled by compaction construction.

The edge joint of the existing asphalt road (usually 30cm-1m in width) is usually constructed with cement or concrete, but cracks and cracks occur over time due to the fatigue resistance and moisture sensitivity of the road and the combination of different types. It can be constructed without covering the silver joint, and even if it is separately constructed using general aggregate or waste aggregate, the above problems can be solved with a kind of combination.

In addition, in one embodiment of the present specification, the concrete composition may be used as a waterproofing agent, a rust preventive agent, and the like. Modified sulfur according to an exemplary embodiment of the present specification has high functionality such as strong chemical resistance, rust prevention, waterproofing, high strength, high adhesion, and quick setting. Therefore, it can be used as a waterproofing, rust-preventing, water-repellent agent, various adhesives, paints, etc. by enhancing specific functionality according to the use.

In one embodiment of the present specification, when the concrete composition is used as a material for a waterproofing agent or a rust preventive agent, a diluent may be further included. In one embodiment, the diluent is ethanol (Ethanol), methanol (Methanol), MEK, toluene (Toluene), m- xylene (m-xylene), p- xylene (P-xylene) from the group It may include any one selected.

In addition, when the concrete composition is used for rust prevention and waterproofing, an additive capable of improving the strength of the rust prevention coating film may be further included when the rust prevention coating is formed.

The concrete composition according to an exemplary embodiment of the present specification can be used in place of epoxy or urethane, is eco-friendly, and does not require overlapping construction of top coat, intermediate coat, and undercoat like existing epoxy or urethane with one-time construction, saving time and cost economical in terms of

Modes for carrying out the invention

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

Preparation of reformed sulfur

At room temperature, 100 g of sulfur and 150 g of oleic acid were added to the polymerization reactor. The temperature of the polymerization reactor was set to about 120° C. with the temperature controller, and the blades of the reactor were stopped until the sulfur and other mixtures became sufficiently liquid. When the mixture was converted to liquid, the blades were rotated to proceed with melt polymerization. When the melt was converted to a liquid state, the temperature of the polymerization reactor was gradually set to about 135 °C in steps of 2 °C to 3 °C while increasing the temperature of the polymerization reactor so that the internal temperature and external temperature of the compound had little deviation (about 5 °C or less). When the temperature of the melt was 160° C. or higher, the state and viscosity of the melt were measured three or more times per hour, and the reaction was terminated when the viscosity reached 10,000 cP to obtain modified sulfur.

Comparative Example 1-1

At room temperature, 150 g of sulfur and 150 g of dicyclopentadiene were added to the polymerization reactor. By setting the temperature to about 120 °C with the temperature controller of the polymerization reactor, melt polymerization was carried out until the sulfur and other mixtures became sufficiently liquid. When the melt was converted into a well-mixed liquid phase, the temperature device of the polymerization reactor was set to about 160°C, and the temperature was gradually increased to 200°C, followed by reaction. The melt was a dark brown liquid compound, and the reaction was terminated at a viscosity of 10,000 cP to obtain solid reformed sulfur after cooling.

The modified sulfur prepared in the comparative example was able to confirm the properties of waterproofing and rust prevention, but due to the foul odor, even when mixing the first sulfur and DCPD, a gas mask should be worn and mixed, and even after the reaction was completed, the gas mask had to be worn with a foul smell. . Therefore, it is difficult to practically apply it in an industrial field.

Wheel Tracking test

In order to confirm the dynamic stability of the modified sulfur prepared in Example 1, 210g of the modified sulfur prepared in Example 1, 2Kg of sand, 1000g of aggregate (13mm), and 210g of MgO were mixed at room temperature for 7 minutes and then mixed with a compactor for asphalt specimens. It was compacted 65 times with a furnace, demolded after 10 minutes, and after 12 hours, a specimen was prepared.

The result of the wheel tracking test on the specimen produced above and the standard straight asphalt (Comparative Example 1-2) and SBS asphalt (Comparative Example 1-3) produced by TWINING, INC through the California TWINING, INC inspection agency is shown. 2 is shown.

Looking at the results of Figure 2, it was confirmed that the modified sulfur according to an exemplary embodiment of the present specification has excellent dynamic stability compared to straight asphalt or SBS modified asphalt.

Example 2

In order to confirm that the concrete composition containing the modified sulfur according to the embodiment of the present specification can be applied in the construction of asphalt road at room temperature, the following experiment was conducted.

Example 2-1

At room temperature, 150 g of sulfur, 150 g of oleic acid, 2 g of pine oil (phytoncide), 2 g of methyl dicyclopentadiene (MDCP), and 2 g of carbon black were administered to the reactor, and the temperature was raised to proceed with melt polymerization at 160 ° C. A liquid phase modified sulfur having a viscosity of 6,000 cP or more was prepared.

After mixing 1000g of aggregate (13mm) at room temperature, 2Kg of sand and 150g of MgO as a hardener, put it in a small aggregate mixer, pour 180g of the modified sulfur prepared above, mix for 7 minutes, and compact 65 times with an asphalt specimen compactor, 10 After a minute elapsed, the mold was demolded, and after one day had elapsed, it was placed in a hot water bath and immersed in water at 60° C. for 1 hour, and then stability and flow values were measured.

It is the weight ratio of 1Kg per specimen, and the measured value of the specimen was stability 12353 and flow value 23. There was hardly any smell of sulfur or other additives during the production of the specimen.

Example 2-2

At room temperature, 150 g of sulfur, 187.5 g of oleic acid, 2 g of pine oil (phytoncide), 2 g of carbon black were administered to the reactor, and the temperature was raised to react at 160°C for 4 hours. The polymerization reaction was terminated at the time point having a cP or higher to prepare a dark brown liquid modified sulfur.

After mixing 1000g of aggregate (13mm), 2Kg of sand and 270g of MgO as a hardener at room temperature, put it in a small aggregate mixer, pour 210g of the modified sulfur and mix for 5 minutes. Then, it was placed in a hot water bath and immersed in water at 60°C for 1 hour. The measured stability value was 15652 and the flow value 18 was measured.

In the preparation of the specimen, it was confirmed that the mixing was well performed even when the mixing time was reduced compared to Example 2-1. This is due to the result of mixing a high content of reformed sulfur.

Example 2-3

150 g of sulfur, 150 g of oleic acid, 2 g of methyl dicyclopentadiene (MDCP), and 2 g of carbon black were administered to the reactor, and the temperature was raised to increase the temperature from 160 ° C to 200 ° C. After reacting, 2 g of phytoncide was administered. It was finished at the time point having a viscosity of 10,000 Cp or more, to prepare a liquid modified sulfur close to black.

Cool the modified sulfur, crush 200 g of rubberized solid form of modified sulfur, add 10 g of diluent ethanol to give fluidity, and first mix 1000 g of aggregate (13 mm), 2 kg of sand and 150 g of MgO as a hardener at room temperature. After that, put it in a small aggregate mixer, pour the diluted modified sulfur and mix for 5 minutes, compact it 65 times with an asphalt specimen compactor. A flow value of 21 of 12286 was measured.

In Example 2-3, it was confirmed that good stability values and flow values were measured even when the content of the curing agent was reduced and mixed in the preparation of the specimen.

The Examples 2-1 to 2-3 relate to a concrete composition used for room temperature asphalt construction. As a result of Examples 2-1 to 2-3, the brittleness, which is the inherent disadvantage of sulfur, is overcome, and the smell is also It was confirmed that it was removed, and it was eco-friendly due to room temperature construction, and it was also confirmed that it was excellent in road maintenance due to improved durability.

In particular, in the case of Example 2-2, it was confirmed that hardening was achieved in 30 minutes and thus suitable for emergency repair. In addition, it was confirmed that the prepared modified sulfur had a fragrant smell of phytoncide.

Example 3

In order to confirm that the concrete composition containing reformed sulfur and waste resources according to the exemplary embodiment of the present specification can be applied in asphalt road construction, the following experiments were conducted.

Example 3-1

750 g of waste glass 315 g of the modified sulfur prepared in Example 1 was mixed with 2000 g of sand, 750 g of gravel (13 mm), and 225 g of hardening material (MgO) and compacted 65 times with an asphalt specimen compactor. 39,496 and 26 flow values were obtained. This indicates a significantly higher value than the standard value of 2500 of the existing normal temperature asphalt stability and can be used in the lower floors of the road.

Example 3-2

Two specimens (A, B) mixed with 240 g of waste vinyl, 315 g of modified sulfur prepared in Example 1, 3000 g of sand, 1260 g of gravel (13mm), and 315 g of hardening material (MgO) were compacted 65 times with an asphalt specimen compactor As a result of measurement after 24 hours, stability A: 14,641, B: 16,515, flow values A:31, B:34 measurement values were obtained. The composition of the crushed waste plastic, which is the final powder, is not the same, so the test results were divided into two types, A and B, and these two also showed significantly higher values than the standard value of 2500 of the existing normal temperature asphalt stability and can be used in the lower floors of the road.

Example 3-3

900 g of steelmaking slug, 315 g of the modified sulfur prepared in Example 1, 3000 g of sand, 600 g of gravel (13 mm), and 225 g of hardening material (MgO) were mixed and compacted 65 times with an asphalt specimen compactor. After 24 hours, the stability was measured as 13,292. and 16 measured values of flow. This indicates a significantly higher value than the standard value of 2500 of the existing normal temperature asphalt stability and can be used in the lower floors of the road.

The results of the stability and flow values of the specimens of Examples 3-1 to 3-3 are the results measured by the test method of KS F 2337:2017 at the Korea Construction Environment Testing Laboratory.

Through the results of Examples 3-1 to 3-3, the modified sulfur according to an exemplary embodiment of the present invention has excellent cohesiveness, cross-linking properties, fluidity, compaction properties, and storage stability, so that crushed waste resources are recycled as a substitute for aggregate I could see what I could do.

Example 4

The water absorption rates of the hydraulic concrete specimen and the general concrete specimen containing modified sulfur prepared in Example 1 were compared. The concrete composition ratio of the concrete specimen was used to produce concrete with a compressive strength of 25 MPa and a slump of 20 cm. This mixture is based on the mixing ratio according to the road pavement repair, bridge pavement and repavement construction guidelines of the Korea Highway Corporation. did it

Example 4-1

After mixing 660 g of Portland cement (Ssangyong general cement), 345 g of water, 55 g of the modified sulfur prepared in Example 1, and 75 g of a water reducing agent, 1000 g of aggregate (13mm) and 2Kg of iron sand were placed in an aggregate mixer and mixed for 10 minutes. After that, it was put in a specimen mold, and after 3 days it disappeared and cured for a total of 28 days.

Comparative Example 4-1

A specimen was prepared in the same manner as in Example 4-1, except that the modified sulfur and water reducing agent were not included in Example 1.

After putting 15L of water in a 20L plastic barrel, the concrete specimens prepared in Example 4-1 and Comparative Example 4-1 were respectively immersed, and the results of measuring the water absorption from 1 month are as shown in FIG. 3 , 3 months The results of measuring the amount of water absorption afterward are shown in Table 1 below.

Example 4-1 Comparative Example 4-1 absorption ratio (%) 0.3 2.6 chemical resistance O X bonding strength (N/cm ² ) <200 X

As a result of Table 1 and FIG. 3, it was confirmed that the hydraulic polymer concrete composition containing modified sulfur according to an exemplary embodiment of the present specification has a small amount of water absorption, excellent chemical resistance, and excellent bonding strength. Example 5

Chemical resistance of concrete compositions containing modified sulfur according to an exemplary embodiment of the present specification was compared.

Examples 5-1 to 5-3

In Example 4-1, a concrete specimen was prepared in the same manner as in Example 4-1, except that 2%, 5%, and 7.5% of the amount of cement administered in a weight ratio of modified sulfur, respectively, was included.

Comparative Example 5-1

A concrete specimen was prepared in the same manner as in Example 5-1, except that the modified sulfur was not included in Example 5-1.

The results of comparison are shown by immersing the concrete specimens prepared in Examples 5-1 to 5-3 and Comparative Example 5-1 in water diluted to a concentration of 30% calcium chloride, 30% sodium chloride and 30% sulfuric acid for 9 months, respectively. 4 is shown.

As a result of FIG. 4 , it was confirmed that the concrete composition including modified sulfur according to an exemplary embodiment of the present specification has excellent chemical resistance compared to the case where modified sulfur is not included. Specifically, even in the case of Example 5-1 containing a relatively small amount of modified sulfur compared to Examples 5-2 and 5-3, it has excellent chemical resistance compared to Comparative Example 5-1 which does not contain modified sulfur. could check

Claims (15)

sulfur and a modifier;
The modifier is oleic acid,
The content of the modifier is 10 parts by weight or more and 450 parts by weight or less, based on 100 parts by weight of the sulfur,
Modified sulfur, having a liquid form at room temperature in a viscosity range of 4,000 cP or more and 25,000 cP or less. delete delete According to claim 1,
The modified sulfur may have radioactivity, or modified sulfur comprising a network structure or a honeycomb structure. delete According to claim 1,
The modified sulfur will be amphiphilic modified sulfur. According to claim 1,
and an additional second modifier. 8. The method of claim 7,
The second modifier is one or more selected from the group consisting of a saturated fatty acid modifier, an unsaturated fatty acid modifier different from oleic acid, an alcohol modifier, an ester modifier, and a dicyclopentadiene modifier. According to claim 1,
The modified sulfur further comprises one or two or more selected from the group consisting of an initiator, a surfactant, a coupling agent, a catalyst, an additive, a crosslinking agent, and a dispersing agent. A first step of mixing an unsaturated fatty acid-based modifier in an amount of 10 parts by weight or more and 450 parts by weight or less based on 100 parts by weight of sulfur, wherein the unsaturated fatty acid-based modifier is oleic acid;
a second step of putting the mixture into a reactor and melting it by heating it to a temperature of 100°C or higher and 130°C or lower;
a third step of raising the temperature of the melt to a temperature of 130 °C or higher and 200 °C or lower; and
A fourth step of terminating the reaction when the viscosity of the melt becomes 6,000 cP or more and 25,000 cp or less at 160 °C,
Having a liquid form in the viscosity range of 4,000 cP or more and 25,000 cP or less at room temperature, a method for producing modified sulfur. delete 11. The method of claim 10,
After the mixture of the second step becomes liquid,
A method for producing modified sulfur that performs the third step. 11. The method of claim 10,
In the third step, the temperature difference between the external temperature of the reactor and the temperature of the melt is 20° C. or less. 11. The method of claim 10,
After the third step, further comprising the step of aging before the fourth step,
The aging step is a method for producing modified sulfur that is carried out at a temperature of 40 ℃ or more. A concrete composition comprising the modified sulfur and aggregate according to any one of claims 1, 4, 6 to 9.

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